Interactions of picosecond laser pulses with organic molecules I. Two-photon fluorescence quenching and singlet states excitation in Rhodamine dyes

Intensity dependent quenching and reversal of the two-photon fluorescence patterns in Rhodamine 6G and DPA, of picosecond pulses from a mode-locked ruby laser have been investigated by measurements of the two-photon fluorescence efficiencies of these dyes. While for Rhodamine 6G there was a marked departure from the square law dependence at high laser intensities, the experimental curve for DPA showed no evidence of quenching. When excited by a mode-locked neodymium: glass laser Rhodamine 6G fluorescence was not quenched at fluxes as high as 5 x 10 30 photons cm -2 s -1 but in Rhodamine B quenching appeared at a laser flux of 3 x 10 27 photons cm -2 s -1 . These quenching results and measurements of the absorption of pulses by Rhodamine 6G, previously excited by second harmonic pulses, are explained by the effects of single photon absorption and stimulated emission from the S 1 and S 2 excited singlet states. A square pulse approximation has been employed to solve the general rate equations and the fitting of the calculated curves to the experimental results gave values for the stimulated emission and absorption cross-sections of the S 1 and S 2 states of Rhodamine 6G and for the relaxation time (~ 2 ps) between the vibrational manifolds of these excited states. Taking into account random phase and amplitude fluctuations of the picosecond pulses, time and space averaged two-photon fluorescence profiles, using these values of the dye parameters, showed quenching and reversal of the patterns for the laser pulse intensities at which these effects were experimentally observed. The possibilities of frequency tunable pulses, of transform-limited durations, from mode-locked dye lasers employed with an electro-optical streak camera of time-resolution equal to that of the pulse durations (~ 2 ps) for time-resolved excited state molecular spectroscopy are briefly considered.